CA1226299A - Process for the co-production of carboxylic acids - Google Patents
Process for the co-production of carboxylic acidsInfo
- Publication number
- CA1226299A CA1226299A CA000429102A CA429102A CA1226299A CA 1226299 A CA1226299 A CA 1226299A CA 000429102 A CA000429102 A CA 000429102A CA 429102 A CA429102 A CA 429102A CA 1226299 A CA1226299 A CA 1226299A
- Authority
- CA
- Canada
- Prior art keywords
- compound
- r1xr2
- acid
- formula
- rhodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Abstract of the Disclosure The invention relates to a process for the co-production of carboxylic acids of formula R1COOH and/or R2COOH and carboxylic acids of the formula R1CH2COOH and/or R2CH2COOH by reacting one or more compounds of the formula R1XR2 in which X represents a
Description
A POSSES FOR TIE CO-PRODUt~ N OF CAF~OXYLIC ACIDS
m e invention relates to a process for the co-production of carboxylic acids and carboxylic acids having one carbon atom more in the molecule. The invention in particular relates to the co-production of acetic acid and prop ionic acid from methyl acetate, dim ethyl ether, acetic android or ethylidene dip acetate.
US patent specification 4,111,982 gives a description of a process for the co-production of acetic acid and prop ionic acid by the reaction of methanol, ethylene carbon monoxide and water in the presence of a rhodium compound and iodine or an iodine compound. One of the starting materials used in this process, ethylene, is a compound which is usually produced from petroleum, whereas interest tends towards a method in which all the starting materials are based on coal (synthesis gas).
From US patent specification 3,769,329 it is known that carboxylic acids can be obtained by carbonylation of alcohols.
The carbonylation is carried out by reacting the alcohol with CO
in the presence of a rhodium compound and bromide or iodine or a brakemen compound or an iodine compound, optionally in the presence of hydrogen. If the reaction is carried out in the presence of water, the starting material used may be not alcohol, but an ester or ether derived therefrom. The c boxlike acid formed contains one carbon atom more than the alcohol or the alcohol-derived moiety present in the ester or ether. Thus the carbonylation for instance of methanol or methyl acetate act cording to US patent specification 3,769,329 leads to the formation of acetic acid. No mention is made in this specific cation of the formation of prop ionic acid.
I, ,, ~L22~9
m e invention relates to a process for the co-production of carboxylic acids and carboxylic acids having one carbon atom more in the molecule. The invention in particular relates to the co-production of acetic acid and prop ionic acid from methyl acetate, dim ethyl ether, acetic android or ethylidene dip acetate.
US patent specification 4,111,982 gives a description of a process for the co-production of acetic acid and prop ionic acid by the reaction of methanol, ethylene carbon monoxide and water in the presence of a rhodium compound and iodine or an iodine compound. One of the starting materials used in this process, ethylene, is a compound which is usually produced from petroleum, whereas interest tends towards a method in which all the starting materials are based on coal (synthesis gas).
From US patent specification 3,769,329 it is known that carboxylic acids can be obtained by carbonylation of alcohols.
The carbonylation is carried out by reacting the alcohol with CO
in the presence of a rhodium compound and bromide or iodine or a brakemen compound or an iodine compound, optionally in the presence of hydrogen. If the reaction is carried out in the presence of water, the starting material used may be not alcohol, but an ester or ether derived therefrom. The c boxlike acid formed contains one carbon atom more than the alcohol or the alcohol-derived moiety present in the ester or ether. Thus the carbonylation for instance of methanol or methyl acetate act cording to US patent specification 3,769,329 leads to the formation of acetic acid. No mention is made in this specific cation of the formation of prop ionic acid.
I, ,, ~L22~9
2 3293-2308 It has now been found that if -the above-mentioned rhodium-catalysed conversion of methyl acetate of dim ethyl ether is carried out under almost anhydric conditions in the presence of hydrogen and at least 2 moles of a carboxylic acid per mole ox the starting compound, this will lead to the co-productlon of acetic acid and prop ionic acid. In addition, small quantities of normal and isobutyric acid may also be formed.
Lowe invention relates to a process for the co-productlon of carboxylic acids of the formula R KIWI and/or R KIWI and carboxylic acids of the formula R SCHICK and/or R SCHICK by reacting one or more compounds of the formula R OR in O O O O R O
If 11 if 11 1 11 which X represents a -O-, -C-O-, -C-O-C- or -C-O-C-O-C-I
moiety and in which Al, R2 and R3 represent similar or dissimilar alkyd, cycloalkyl, aureole, aralkyl or alkaryl groups which may be substituted with one or more halogen atoms, with carbon monoxide and hydrogen in the presence of a rhodium catalyst and an iodide anywhere bromide source, characterized in that the reaction is carried out under substantially an hydrous conditions and in the presence - per mole of the compound RlXR2 - of at least 2 moles of a carboxylic acid of the formula R COO, in which R represents an alkyd, cycloalkyl, aureole, aralkyl or alkaryl group which may be Jo - ~2~:6299 - pa -substituted with one or more halogen atoms, and using a molar ratio of hydrogen to carbon monoxide of at least 1:10.
The carbonylation of methyl acetate or dim ethyl ether under almost anhydric conditions has been described in the literature, but owing to the use of different reaction conditions, the products obtained therein are different from those obtained in the process according to the invention. For instance, the preparation of acetic android by the reaction of methyl acetate or dim ethyl ether with CO in the presence of methyl iodide and a compound of a Group VIII metal is known from United Kingdom patent specification 1,468,9~0. The reaction is carried out under anhydric conditions and, as can be seen from the examples, in the absence of earboxylic acids. In this patent specification ~26~
no mention is made of the formation of acetic acid or prop ionic acid.
UK patent specification 1,523,346 relates to a similar process for the preparation of acetic android by carbonylation of methyl acetate. It is stated that the presence of hydrogen can have a favorable effect on the course of the reaction, since it suppresses the formation of soot and carbon dioxide, but that it stimulates the formation of the by-product acetic acid. However, example 13 shows that the quantity of acetic acid formed in the presence of hydrogen it considerably smaller than the quantity used in the process according to the present invention; no mention is made of the formation of prop ionic acid.
From UK patent specification 1,538,782 it is known that ethylidene diacetate can be prepared by reaction of methyl acetate and/or dim ethyl ether with carbon oxide and hod m gun under anhydric conditions in the presence of a Group VIII noble metal catalyst, a bromide or an iodide and a promoter. m is process leads to the formation of acetic android, acetaldehyde and acetic acid as by-product, but the quantity of acetic acid formed is smaller than the minimum required in the process according to the present invention to bring about the formation of prop ionic acid. Further it is seen from Examples V and VIII
of UK patent specification 1,538,782 that for obtaining reaction products the presence of a promoter is essential; in the access according to the invention this is not the case.
It is not known what mechanism governs the reaction or reactions involved in the process according to the invention.
m e "overall" reaction which takes place when methyl acetate is the starting material may be represented by the following reaction equation:
H3COOCH3 + 2 CO + 2 Ho CH3CH2COOH + SCHICK.
When dim ethyl ether, ethylidene diacetate or acetic android is the starting material, the respective reaction equations will be:
~2;2~299 CH30CH3 + 3 CO + 2 H ` OH OH COO + OH COO
CH3CH(OCOCH3)2 + 2 CO + 3 Ho ~-~ 2 CH3CH2COOH + SCHICK,
Lowe invention relates to a process for the co-productlon of carboxylic acids of the formula R KIWI and/or R KIWI and carboxylic acids of the formula R SCHICK and/or R SCHICK by reacting one or more compounds of the formula R OR in O O O O R O
If 11 if 11 1 11 which X represents a -O-, -C-O-, -C-O-C- or -C-O-C-O-C-I
moiety and in which Al, R2 and R3 represent similar or dissimilar alkyd, cycloalkyl, aureole, aralkyl or alkaryl groups which may be substituted with one or more halogen atoms, with carbon monoxide and hydrogen in the presence of a rhodium catalyst and an iodide anywhere bromide source, characterized in that the reaction is carried out under substantially an hydrous conditions and in the presence - per mole of the compound RlXR2 - of at least 2 moles of a carboxylic acid of the formula R COO, in which R represents an alkyd, cycloalkyl, aureole, aralkyl or alkaryl group which may be Jo - ~2~:6299 - pa -substituted with one or more halogen atoms, and using a molar ratio of hydrogen to carbon monoxide of at least 1:10.
The carbonylation of methyl acetate or dim ethyl ether under almost anhydric conditions has been described in the literature, but owing to the use of different reaction conditions, the products obtained therein are different from those obtained in the process according to the invention. For instance, the preparation of acetic android by the reaction of methyl acetate or dim ethyl ether with CO in the presence of methyl iodide and a compound of a Group VIII metal is known from United Kingdom patent specification 1,468,9~0. The reaction is carried out under anhydric conditions and, as can be seen from the examples, in the absence of earboxylic acids. In this patent specification ~26~
no mention is made of the formation of acetic acid or prop ionic acid.
UK patent specification 1,523,346 relates to a similar process for the preparation of acetic android by carbonylation of methyl acetate. It is stated that the presence of hydrogen can have a favorable effect on the course of the reaction, since it suppresses the formation of soot and carbon dioxide, but that it stimulates the formation of the by-product acetic acid. However, example 13 shows that the quantity of acetic acid formed in the presence of hydrogen it considerably smaller than the quantity used in the process according to the present invention; no mention is made of the formation of prop ionic acid.
From UK patent specification 1,538,782 it is known that ethylidene diacetate can be prepared by reaction of methyl acetate and/or dim ethyl ether with carbon oxide and hod m gun under anhydric conditions in the presence of a Group VIII noble metal catalyst, a bromide or an iodide and a promoter. m is process leads to the formation of acetic android, acetaldehyde and acetic acid as by-product, but the quantity of acetic acid formed is smaller than the minimum required in the process according to the present invention to bring about the formation of prop ionic acid. Further it is seen from Examples V and VIII
of UK patent specification 1,538,782 that for obtaining reaction products the presence of a promoter is essential; in the access according to the invention this is not the case.
It is not known what mechanism governs the reaction or reactions involved in the process according to the invention.
m e "overall" reaction which takes place when methyl acetate is the starting material may be represented by the following reaction equation:
H3COOCH3 + 2 CO + 2 Ho CH3CH2COOH + SCHICK.
When dim ethyl ether, ethylidene diacetate or acetic android is the starting material, the respective reaction equations will be:
~2;2~299 CH30CH3 + 3 CO + 2 H ` OH OH COO + OH COO
CH3CH(OCOCH3)2 + 2 CO + 3 Ho ~-~ 2 CH3CH2COOH + SCHICK,
3 3 CO + 2 Ho CH3cH2cooH + OH COO
Independent of each other, R , R , R and R represent alkyd, cycloalkyl, aureole, aralkyl or alkaryl groups which optionally may be substituted with one or more halogen atoms. Preferably the hydrocarbon groups are unsubstituted and preferably they contain 1-20, in particular 1-6 carbon atoms.
Naturally, the composition of the reaction product obtained in the process according to the invention is dependent on the RlXR2 compound chosen. In order to keep this composition as simple as possible, the compound RlXR2 preferably used is one in which the groups R and R2 are identical. Examples of compounds of this type that are particularly preferred are methyl acetate, dim ethyl ether, ethylidene acetate and acetic android.
If compound RlXR2 is an ester, it should be taken into account that, as a side reaction, some ester interchange between the ester and the carboxylic acid R4CoOH may occur. Therefore it is preferred to use a carboxylic acid R COO which corresponds with the acid-derived moiety of the ester. Thus, the reaction between, for instance, methyl acetate, CO and Ho is preferably carried out in acetic acid.
If in the compound R OR moiety X represents the group O O R3 o If 11 it i ii -o-, -C-O-C- or -C-O-C-O-C -go - pa -then preference is given to the use of a carboxylic acid R4CoOH
in which group R it identical to Al or R2, which groups are preferably identical as well, as mentioned herein before.
The molar ratio of the carboxylic acid R4CoOH to compound RlXR2 generally lies between 2:1 and 20:1, preferably between ~2~2g9 3:1 and 15:1 and most preferably between 4:1 and 15:1. However, larger quantities of the carboxylic acid R4CoOH can be used.
The rhodium catalyst may be of any suitable type. Suitable catalysts are, for instance, rhodium oxide and rhodium hydroxide, rhodium salts of mineral acids, such as hydrogen chloride, nitric acid and sulfuric acid and rhodium salts of organic acids, preferably of Al Kane carboxylic acids having 1-20 carbon clams. The rhodium may also be complexes in a zero-valent form with ligands such as carbon monoxide, acetylacetone or organic compounds of nitrogen, phosphorus, arsenic or antimony.
m e quantity of rhodium catalyst preferably lies between 0.01 and 10, in particular between 0.05 and em per to of compound RlXR2. Larger or smaller quantities can, however, be used.
m e iodide or bromide source may be elementary iodine or bromide, a compound ROY or R5Br, in which the moiety R5 is preferably an alkyd group with 1-12 carbon atoms or a cycle-aIkyl, aureole, aralkyl or alkaryl group having not more than 12 carbon atoms, or an azalea iodide or azalea bromide R5COI or R5COBr in which R5 has the above-mentioned m axing, hydrogen iodide or hydrogen bromide, an alkali metal iodide or an alkaline earth metal iodide, for instance lithium iodide or sodium iodide or an alkali metal bromide or an alkaline earth metal bromide.
If desired, two or more iodide and/or bromide sources may be used.
m e quantity of the-iodide or bromide source added to the reaction mixture is not critical. The number of gram atoms of iodine or bromide added in the elementary form or as iodide or bromide lies, for instance, between 0.1 and 200, preferably between 5 and 50 gram atoms per gram atom of rhodium.
The process according to the invention is preferably carried out in the presence of one or more promoters. Suitable prompters are the oxides of amine, phosphines, arsines and stubbiness. A group of promoters used by preference are those ~L2~29~3 having the formula YZR'R " R " ', in which Y represents oxygen, Selfware or selenium, Z represents phosphorus, antimony or arsenic and the reties R', R " , R " ' independent of one another each represents a hydrogen atom or an alkyd, cyclical, aureole or aralkyl group. m eye groups may be substituted, if required, with one or no substituents which under the reaction conditions are m oft for instant ox , halogen atoms. The pieties R " and Al " together may represent an alkaline group which preferably has not more than 20 carbon atoms. Each aIkyl group preferably conic m s not more than 20 carbon atoms, Mach cycle-aIkyl group preferably contains not more than 7 carbon atoms and each aureole group is preferably a phenol group. Promoters in which R', R " and R " ' independent of one another represent an aureole group or a phenol group are specially preferred. The moieties R', R " and R " ' preferably are identical, Z preferably represents a phosphorus clam. Oxides, sulfides and solenoids of phosphines, arsines or stubbiness containing two or more phosphorus, arsenic or antimony atoms are also suitable as prompters.
Another group of suitable promoters is made up of compounds of the formula YZ(~R')(OR "O'ER " '), in which Y, Z, R', R " and R " ' have the meanings stated herein before. This group includes for instance esters of phosphoric acid and thiophosphoric acid.
Also suitable are compounds of the formula YE Tory I by rock ] in which Y, Z, R', R" and R " ' have the meanings stated herein before, each of a, b and c is 0 or 1, and a b c equals 1 or 2.
Examples of suitable promoters are trimethylphosphine oxide, tri-n-butylphosphine oxide, triphenylphosphine oxide, tri-p-tolylphosphine oxide, tetraphenyl dim ethylene diphosphine dioxide (diphosdioxide), tetraphenyl trim ethylene diphosphine dioxide, tri-n-butyl phosphate, triphenyl phosphate, dimet}lyl methylphosphonate, diphenyl methylphosphonate, methyl methyl phosphonate, methyl diethylphosphonate and methyl diphenyl-phosphonate~ trimethylarsine oxide, tri-isopropylstibine oxide, tricyclohexylarsine oxide, triphenylstibine oxide, diphenyl-ethylarsine oxide, ethylenebis-(diphenylarsine) oxide, in-phenylphosphine sulfide and tributylphosphine sulfide. Examples of suitable N-amine oxides are pardon N-oxide, the picoline N-oxides and trimethylamine N-oxide.
Complexes which may be formed by the reaction of oxides, sulfides or solenoids of phosphines, arsines or stubbiness with alkyd halides or hydrogen halides, such as E (C H5)3AsO-H-OAs(C2H5)3] I or [(C6H5)3 6 5 3 3 are also suitable promoters.
The above-mentioned promoters are usually used in catalytic quantities. These quantities are not critical. Suitable quanta-ties lie between, for example, 0.1 and 100, preferably between 0.5 and 10 mole per gram atom of rhodium.
Further, the process may suitably be carried out in the presence of small quantities - for instance of up to 100 equip-alerts per gram atom of rhodium - of a strong acid as the promoter.
Suitable strong acids are those which, in an aqueous solution, at 20C have a pea lower than 3.5, for instance p-toluenesulphonic acid or trifluoromethanesulphonic acid or mineral acids, such as hydrochloric acid, sulfuric acid or perchloric acid.
The process is carried out under substantially an hydrous conditions. However, such small quantities of water as may be present in commercially available starting materials, e.g. rhodium (III) chloride trihydrate, are permissible. The reaction mixture preferably contains not more than 2, in particular not more than 0.2, ow water.
The process according to the invention may be carried out either in the liquid phase or in the gaseous phase. The hydrogen 62g~
- pa -and the carbon monoxide may be added simultaneously if desired.
Although usually carbon monoxide and hydrogen are added in more or less equimolar quantities, the molar ratios between the two compounds may vary within wide limits, for instance in the range of from 10:1 to 1:10. The carbon monoxide hydrogen molar ratio preferably lies between 1:0.5 and 1:3. Inert gases, such as 29~
nitrogen, noble gases, carbon dioxide or methane may optionally be present in the reaction mixture. m e process may be carried out bushes, count m usual or semi-continuously.
m e process according to the invention is preferably carried out at a temperature between 50 and 300C, in particular between 50 and 200C and most preferably between 125 and 175C.
Either low pressure of, for instance, S bar or high pressures of, for instance, 1000 bar may be used. Usually high pressures are not economical on account of the investment and energy costs involved. m e pressure preferably lies between 20 and 100 bar.
The process according to the invention may be carried out in the presence of an additional solvent, if desired. However, compound RlXR2, such as methyl acetate, ethyl acetate, methyl preappoint, ethyl preappoint, dim ethyl ether, deathly ether or methyl t-butyl ether and/or the carboxylic acid R COO, for instance acetic acid or prop ionic acid, may in itself serve as a solvent as well. In that case it should naturally be en Æ Ed that the c æ~cxylic acid R4CoOH is present in such a proportion to cc~x~md RlXR2 as is required according to the invention. Sup W to additional solvents include cyclic ethers, such as tetrahydrofuran, Dixon, Dixon and the dioxolanes, sulphones and sulphoxides, such as dim ethyl cellophane, sulpholane, 2-methyl sulpholane, 3-methyl sulpholane, dim ethyl sulphoxide and deathly sulphoxide. Butyrolacetone it a very suitable solvent. The additional solvent is generally used in quantities sufficient to keep the reaction mixture homogeneous -for instance 5-20 TV, calculated on the total reaction mixture.
The reaction mixture obtained in the process according to the invention may be processed by known techniques, such as fractional distillation. If desired, the products may be subjected to further purification treatments.
With respect both to the starting materials and to conversion of the acids formed, the process may be integrated into existing processes. For instance the process is excel-I
gently suitable for the co-production of acetic acid an prop ionic acid from methyl acetate which in its turn can be prep æ Ed by carbonylation of methanol. Whilst the prop ionic acid obtained may be of interest in itself, the acetic acid formed as a by-product can be esterified with methanol to form methyl acetate, which compound can be recirculated to the reactor.
EXAMPLE I
The process was carried out in a 300 ml magnetically stirred Hostile C autoclave (Hostile is a trade mark) containing 35 ml (0.6 mole) acetic acid and 1 mole rhodium (III) chloride trihydrate and methyl acetate, methyl iodide or lithium iodide and optionally triphenylphosphine, triphenyl-phosphine oxide, dim ethyl methylphosphonate or Tulane sulphonic acid in the quantities given in Table A. The autoclave was flushed with carbon monoxide and then filled with a mixture of carbon monoxide and hydrogen (molar ratio 1:1) under pros Æ e.
The temperatures and pressures used æ e given in Table A. The autoclave was kept at the temperature mentioned for 15 hours.
Subsequently the reaction n~rbure was cooled and analyzed by mans of gas-liquid chromatography. m e methyl acetate conversion was invariably 100%. The yields of prop ionic acid and of normal and isobutyric acid are given in Table A in em, calculated on methyl acetate converted. All the experiments in addition yielded acetic acid as a co-product in at least equimolar quantities calculated on prop ionic acid produced.
~2~2~
Jo, Jo In us Jo c.) I us In O O Lo ,.
o o CO o o owe Us U o Us o o o o o o o or In ED Us JO ED
D o Jo o o I' o o r Jo I I
no ago o o o o o I m , Jo _ _ _ _ _ _ _ _ _ no I
C ~.~
z W 1` CO a o 2Ç~2~
O R I, I
Lowe o o o Jo .
Us ,¢ I ,, ,, ,1 us l H
lot 'root Jo .
I I Us Us O C) I
_ X X U H
H H H
lo Al 11 11 H H I H
~226~9 Comparison of Experiments 1 and 2 shows that raising the acetic acid methyl acetate molar ratio from 3:1 to 6:1 increases thy yield of prop ionic acid. Experiment 11 skews that when said molar ratio is lower than 2:1, no prop ionic acid is formed.
Experiment 12 shows that not even the presence of the active promoter p-toluenesulphonic acid allows prop ionic acid to be formed in the absence of acetic acid. Experiments 13 and 14 show that under the reaction conditions used compounds of Rut and Pod do not catalyze the desired conversion.
EXAMPLE II
The process was carried out in a 300 ml magnetically stirred ~Iastelloy C autoclave (Hostile is a trade mark) containing 35 ml of an Al Kane carboxylic acid, 1 mole rhodium (III) chloride trihydrate, 15 mole methyl iodide and 4 mmDle triphenylphosphine oxide, and 7.5 ml methyl acetate, methyl preappoint ethyl preappoint, acetic android or ethylidene diacetate. The autoclave was flushed with carbon monoxide and subsequently filled with a mixture of carbon monoxide and hydrogen (molar ratio 1:1) at a pressure of 60 bar. The auto-crave was kept at a temperature of 160C for 15 hours. Then the reaction mixture was cooled and analyzed by gas-liquid chromatography. Conversion was 100% in the experiments using methyl acetate, methyl preappoint, acetic android and ethylidene diacetate and 80% in the experiment using ethyl preappoint. m e awaken carboxylic acids and the concentrations in which the v æ ions carboxylic acids were present in the reaction mixture are given in Table B.
i;299 TABLE B
Al Kane carboxylic acid carboxylic concentrations acid in reaction mixture, ow . _ . _ _ methyl acetate prop ionic acid acetic acid 19 prop ionic acid 67 n-butyric acid 6.3 isobutyric acid 4.3 methyl preappoint acetic acid acetic acid 74 prop ionic acid 22 n-butyric acid 1.3 isobutyric acid 1.2 methyl preappoint prop ionic acid acetic acid 9 prop ionic acid 78 n-butyric acid 6 isobutyric acid 4.5 ethyl prcpionate prop ionic acid prop ionic acid 87 n-butyric acid 3.5 isobu~yric acid 2.6 acetic android acetic acid acetic acid 87 prop ionic acid 9.5 n-butyric acid 0.5 - isobutyric acid 0.5 ethylidene acetic acid acetic acid 85 diacetate prop ionic acid 13.1 n-butyric acid 1.0 isokutyric acid 1.0
Independent of each other, R , R , R and R represent alkyd, cycloalkyl, aureole, aralkyl or alkaryl groups which optionally may be substituted with one or more halogen atoms. Preferably the hydrocarbon groups are unsubstituted and preferably they contain 1-20, in particular 1-6 carbon atoms.
Naturally, the composition of the reaction product obtained in the process according to the invention is dependent on the RlXR2 compound chosen. In order to keep this composition as simple as possible, the compound RlXR2 preferably used is one in which the groups R and R2 are identical. Examples of compounds of this type that are particularly preferred are methyl acetate, dim ethyl ether, ethylidene acetate and acetic android.
If compound RlXR2 is an ester, it should be taken into account that, as a side reaction, some ester interchange between the ester and the carboxylic acid R4CoOH may occur. Therefore it is preferred to use a carboxylic acid R COO which corresponds with the acid-derived moiety of the ester. Thus, the reaction between, for instance, methyl acetate, CO and Ho is preferably carried out in acetic acid.
If in the compound R OR moiety X represents the group O O R3 o If 11 it i ii -o-, -C-O-C- or -C-O-C-O-C -go - pa -then preference is given to the use of a carboxylic acid R4CoOH
in which group R it identical to Al or R2, which groups are preferably identical as well, as mentioned herein before.
The molar ratio of the carboxylic acid R4CoOH to compound RlXR2 generally lies between 2:1 and 20:1, preferably between ~2~2g9 3:1 and 15:1 and most preferably between 4:1 and 15:1. However, larger quantities of the carboxylic acid R4CoOH can be used.
The rhodium catalyst may be of any suitable type. Suitable catalysts are, for instance, rhodium oxide and rhodium hydroxide, rhodium salts of mineral acids, such as hydrogen chloride, nitric acid and sulfuric acid and rhodium salts of organic acids, preferably of Al Kane carboxylic acids having 1-20 carbon clams. The rhodium may also be complexes in a zero-valent form with ligands such as carbon monoxide, acetylacetone or organic compounds of nitrogen, phosphorus, arsenic or antimony.
m e quantity of rhodium catalyst preferably lies between 0.01 and 10, in particular between 0.05 and em per to of compound RlXR2. Larger or smaller quantities can, however, be used.
m e iodide or bromide source may be elementary iodine or bromide, a compound ROY or R5Br, in which the moiety R5 is preferably an alkyd group with 1-12 carbon atoms or a cycle-aIkyl, aureole, aralkyl or alkaryl group having not more than 12 carbon atoms, or an azalea iodide or azalea bromide R5COI or R5COBr in which R5 has the above-mentioned m axing, hydrogen iodide or hydrogen bromide, an alkali metal iodide or an alkaline earth metal iodide, for instance lithium iodide or sodium iodide or an alkali metal bromide or an alkaline earth metal bromide.
If desired, two or more iodide and/or bromide sources may be used.
m e quantity of the-iodide or bromide source added to the reaction mixture is not critical. The number of gram atoms of iodine or bromide added in the elementary form or as iodide or bromide lies, for instance, between 0.1 and 200, preferably between 5 and 50 gram atoms per gram atom of rhodium.
The process according to the invention is preferably carried out in the presence of one or more promoters. Suitable prompters are the oxides of amine, phosphines, arsines and stubbiness. A group of promoters used by preference are those ~L2~29~3 having the formula YZR'R " R " ', in which Y represents oxygen, Selfware or selenium, Z represents phosphorus, antimony or arsenic and the reties R', R " , R " ' independent of one another each represents a hydrogen atom or an alkyd, cyclical, aureole or aralkyl group. m eye groups may be substituted, if required, with one or no substituents which under the reaction conditions are m oft for instant ox , halogen atoms. The pieties R " and Al " together may represent an alkaline group which preferably has not more than 20 carbon atoms. Each aIkyl group preferably conic m s not more than 20 carbon atoms, Mach cycle-aIkyl group preferably contains not more than 7 carbon atoms and each aureole group is preferably a phenol group. Promoters in which R', R " and R " ' independent of one another represent an aureole group or a phenol group are specially preferred. The moieties R', R " and R " ' preferably are identical, Z preferably represents a phosphorus clam. Oxides, sulfides and solenoids of phosphines, arsines or stubbiness containing two or more phosphorus, arsenic or antimony atoms are also suitable as prompters.
Another group of suitable promoters is made up of compounds of the formula YZ(~R')(OR "O'ER " '), in which Y, Z, R', R " and R " ' have the meanings stated herein before. This group includes for instance esters of phosphoric acid and thiophosphoric acid.
Also suitable are compounds of the formula YE Tory I by rock ] in which Y, Z, R', R" and R " ' have the meanings stated herein before, each of a, b and c is 0 or 1, and a b c equals 1 or 2.
Examples of suitable promoters are trimethylphosphine oxide, tri-n-butylphosphine oxide, triphenylphosphine oxide, tri-p-tolylphosphine oxide, tetraphenyl dim ethylene diphosphine dioxide (diphosdioxide), tetraphenyl trim ethylene diphosphine dioxide, tri-n-butyl phosphate, triphenyl phosphate, dimet}lyl methylphosphonate, diphenyl methylphosphonate, methyl methyl phosphonate, methyl diethylphosphonate and methyl diphenyl-phosphonate~ trimethylarsine oxide, tri-isopropylstibine oxide, tricyclohexylarsine oxide, triphenylstibine oxide, diphenyl-ethylarsine oxide, ethylenebis-(diphenylarsine) oxide, in-phenylphosphine sulfide and tributylphosphine sulfide. Examples of suitable N-amine oxides are pardon N-oxide, the picoline N-oxides and trimethylamine N-oxide.
Complexes which may be formed by the reaction of oxides, sulfides or solenoids of phosphines, arsines or stubbiness with alkyd halides or hydrogen halides, such as E (C H5)3AsO-H-OAs(C2H5)3] I or [(C6H5)3 6 5 3 3 are also suitable promoters.
The above-mentioned promoters are usually used in catalytic quantities. These quantities are not critical. Suitable quanta-ties lie between, for example, 0.1 and 100, preferably between 0.5 and 10 mole per gram atom of rhodium.
Further, the process may suitably be carried out in the presence of small quantities - for instance of up to 100 equip-alerts per gram atom of rhodium - of a strong acid as the promoter.
Suitable strong acids are those which, in an aqueous solution, at 20C have a pea lower than 3.5, for instance p-toluenesulphonic acid or trifluoromethanesulphonic acid or mineral acids, such as hydrochloric acid, sulfuric acid or perchloric acid.
The process is carried out under substantially an hydrous conditions. However, such small quantities of water as may be present in commercially available starting materials, e.g. rhodium (III) chloride trihydrate, are permissible. The reaction mixture preferably contains not more than 2, in particular not more than 0.2, ow water.
The process according to the invention may be carried out either in the liquid phase or in the gaseous phase. The hydrogen 62g~
- pa -and the carbon monoxide may be added simultaneously if desired.
Although usually carbon monoxide and hydrogen are added in more or less equimolar quantities, the molar ratios between the two compounds may vary within wide limits, for instance in the range of from 10:1 to 1:10. The carbon monoxide hydrogen molar ratio preferably lies between 1:0.5 and 1:3. Inert gases, such as 29~
nitrogen, noble gases, carbon dioxide or methane may optionally be present in the reaction mixture. m e process may be carried out bushes, count m usual or semi-continuously.
m e process according to the invention is preferably carried out at a temperature between 50 and 300C, in particular between 50 and 200C and most preferably between 125 and 175C.
Either low pressure of, for instance, S bar or high pressures of, for instance, 1000 bar may be used. Usually high pressures are not economical on account of the investment and energy costs involved. m e pressure preferably lies between 20 and 100 bar.
The process according to the invention may be carried out in the presence of an additional solvent, if desired. However, compound RlXR2, such as methyl acetate, ethyl acetate, methyl preappoint, ethyl preappoint, dim ethyl ether, deathly ether or methyl t-butyl ether and/or the carboxylic acid R COO, for instance acetic acid or prop ionic acid, may in itself serve as a solvent as well. In that case it should naturally be en Æ Ed that the c æ~cxylic acid R4CoOH is present in such a proportion to cc~x~md RlXR2 as is required according to the invention. Sup W to additional solvents include cyclic ethers, such as tetrahydrofuran, Dixon, Dixon and the dioxolanes, sulphones and sulphoxides, such as dim ethyl cellophane, sulpholane, 2-methyl sulpholane, 3-methyl sulpholane, dim ethyl sulphoxide and deathly sulphoxide. Butyrolacetone it a very suitable solvent. The additional solvent is generally used in quantities sufficient to keep the reaction mixture homogeneous -for instance 5-20 TV, calculated on the total reaction mixture.
The reaction mixture obtained in the process according to the invention may be processed by known techniques, such as fractional distillation. If desired, the products may be subjected to further purification treatments.
With respect both to the starting materials and to conversion of the acids formed, the process may be integrated into existing processes. For instance the process is excel-I
gently suitable for the co-production of acetic acid an prop ionic acid from methyl acetate which in its turn can be prep æ Ed by carbonylation of methanol. Whilst the prop ionic acid obtained may be of interest in itself, the acetic acid formed as a by-product can be esterified with methanol to form methyl acetate, which compound can be recirculated to the reactor.
EXAMPLE I
The process was carried out in a 300 ml magnetically stirred Hostile C autoclave (Hostile is a trade mark) containing 35 ml (0.6 mole) acetic acid and 1 mole rhodium (III) chloride trihydrate and methyl acetate, methyl iodide or lithium iodide and optionally triphenylphosphine, triphenyl-phosphine oxide, dim ethyl methylphosphonate or Tulane sulphonic acid in the quantities given in Table A. The autoclave was flushed with carbon monoxide and then filled with a mixture of carbon monoxide and hydrogen (molar ratio 1:1) under pros Æ e.
The temperatures and pressures used æ e given in Table A. The autoclave was kept at the temperature mentioned for 15 hours.
Subsequently the reaction n~rbure was cooled and analyzed by mans of gas-liquid chromatography. m e methyl acetate conversion was invariably 100%. The yields of prop ionic acid and of normal and isobutyric acid are given in Table A in em, calculated on methyl acetate converted. All the experiments in addition yielded acetic acid as a co-product in at least equimolar quantities calculated on prop ionic acid produced.
~2~2~
Jo, Jo In us Jo c.) I us In O O Lo ,.
o o CO o o owe Us U o Us o o o o o o o or In ED Us JO ED
D o Jo o o I' o o r Jo I I
no ago o o o o o I m , Jo _ _ _ _ _ _ _ _ _ no I
C ~.~
z W 1` CO a o 2Ç~2~
O R I, I
Lowe o o o Jo .
Us ,¢ I ,, ,, ,1 us l H
lot 'root Jo .
I I Us Us O C) I
_ X X U H
H H H
lo Al 11 11 H H I H
~226~9 Comparison of Experiments 1 and 2 shows that raising the acetic acid methyl acetate molar ratio from 3:1 to 6:1 increases thy yield of prop ionic acid. Experiment 11 skews that when said molar ratio is lower than 2:1, no prop ionic acid is formed.
Experiment 12 shows that not even the presence of the active promoter p-toluenesulphonic acid allows prop ionic acid to be formed in the absence of acetic acid. Experiments 13 and 14 show that under the reaction conditions used compounds of Rut and Pod do not catalyze the desired conversion.
EXAMPLE II
The process was carried out in a 300 ml magnetically stirred ~Iastelloy C autoclave (Hostile is a trade mark) containing 35 ml of an Al Kane carboxylic acid, 1 mole rhodium (III) chloride trihydrate, 15 mole methyl iodide and 4 mmDle triphenylphosphine oxide, and 7.5 ml methyl acetate, methyl preappoint ethyl preappoint, acetic android or ethylidene diacetate. The autoclave was flushed with carbon monoxide and subsequently filled with a mixture of carbon monoxide and hydrogen (molar ratio 1:1) at a pressure of 60 bar. The auto-crave was kept at a temperature of 160C for 15 hours. Then the reaction mixture was cooled and analyzed by gas-liquid chromatography. Conversion was 100% in the experiments using methyl acetate, methyl preappoint, acetic android and ethylidene diacetate and 80% in the experiment using ethyl preappoint. m e awaken carboxylic acids and the concentrations in which the v æ ions carboxylic acids were present in the reaction mixture are given in Table B.
i;299 TABLE B
Al Kane carboxylic acid carboxylic concentrations acid in reaction mixture, ow . _ . _ _ methyl acetate prop ionic acid acetic acid 19 prop ionic acid 67 n-butyric acid 6.3 isobutyric acid 4.3 methyl preappoint acetic acid acetic acid 74 prop ionic acid 22 n-butyric acid 1.3 isobutyric acid 1.2 methyl preappoint prop ionic acid acetic acid 9 prop ionic acid 78 n-butyric acid 6 isobutyric acid 4.5 ethyl prcpionate prop ionic acid prop ionic acid 87 n-butyric acid 3.5 isobu~yric acid 2.6 acetic android acetic acid acetic acid 87 prop ionic acid 9.5 n-butyric acid 0.5 - isobutyric acid 0.5 ethylidene acetic acid acetic acid 85 diacetate prop ionic acid 13.1 n-butyric acid 1.0 isokutyric acid 1.0
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the co-production of carboxylic acids of formula R1COOH and/or R2COOH and carboxylic acids of the formula R1CH2COOH and/or R2CH2COOH by reacting one or more compounds of the formula R1XR2 in which X represents a moiety and in which R1, R2 and R3 represent similar or dissimilar alkyl, cycloalkyl, aryl, aralkyl or alkaryl groups, which may be substituted with one or more halogen atoms, with carbon monoxide and hydrogen in the presence of a rhodium catalyst and an iodide and/or bromide source, characterized in that the reaction is carried out under substantially anhydrous conditions and in the presence - per mole of the compound R1XR2 - of at least 2 moles of a carboxylic acid of the formula R4COOH, in which R4 represents an alkyl, cycloalkyl, aryl, aralkyl or alkaryl group which may be substituted with one or more halogen atoms, and using a molar ratio of hydrogen to carbon monoxide of at least 1:10.
2. A process as claimed in claim 1, characterized in that R1, R2, R3 and R4 are unsubstituted and contain 1-20 carbon atoms.
3. A process as claimed in claim 1, characterized in that R1 and R2 are identical.
4. A process as claimed in claim 1, characterized in that the compound R1XR2 is methyl acetate, dimethyl ether, ethylidene diacetate or acetic anhydride.
5. A process as claimed in claim 1, characterized in that when compound R1XR2 is an ester, the carboxylic acid R4COOH
corresponds with the acid-derived moiety of the ester and when in compound R1XR2 the moiety X represents the group R4 of carboxylic acid R4COOH is identical with R1 or R2.
corresponds with the acid-derived moiety of the ester and when in compound R1XR2 the moiety X represents the group R4 of carboxylic acid R4COOH is identical with R1 or R2.
6. A process as claimed in claim 1, characterized in that the molar ratio of carboxylic acid R4COOH to compound R1XR2 lies between 2:1 and 20:1.
7. A process as claimed in claim 5, characterized in that the molar ratio of carboxylic acid R4COOH to compound R1XR2 lies between 3:1 and 15:1.
8. A process as claimed in claim 1, characterized in that the quantity of rhodium catalyst lies between 0.01 and 10 moles per mole of compound R1XR2.
9. A process as claimed in claim 1, characterized in that per gram atom of rhodium 0.01-200 gram atom of iodine and/or bromine in elementary form or as iodide and/or bromide is present in the reaction mixture.
10. A process as claimed in claim 1, characterized in that the process is carried out in the presence of a compound having the formula YZR'R''R''', YZ(OR')(OR'')(OR''') or YZ[(O)aR'][(O)bR''][(O)cR'''], in which Y is oxygen, sulphur or selenium, Z represents phosphorus antimony or arsenic and the moieties R', R'' and R''' independent of one another, each represent a hydrogen atom or an alkyl, cycloalkyl, aryl or aralkyl group which may be substituted with in inert substituent, a, b and c each are 0 or 1, and a + b + c equals 1 or 2 as promoter.
11. A process as claimed in claim 10, characterized in that the quantity of promoter lies between 0.1 and 100 mole per gram atom of rhodium.
12. A process as claimed in claim 1, characterized in that the process is carried out in the presence of up to 100 equivalents per gram atom of rhodium, of an acid which, in an aqueous solution, at 20°C has a pKa of less than 3.5.
13. A process as claimed in claim 1, characterized in that the process is carried out at a temperature in the range between 50 and 300°C and a pressure in the range between 20 and 100 bar.
14. A process as claimed in claim 1, characterized in that the reaction mixture contains less than 2 %w water.
15. A process as claimed in claim 1, characterized in that the reaction mixture contains less than 0.2 %w water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8202493 | 1982-06-18 | ||
| NL8202493 | 1982-06-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1226299A true CA1226299A (en) | 1987-09-01 |
Family
ID=19839911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000429102A Expired CA1226299A (en) | 1982-06-18 | 1983-05-27 | Process for the co-production of carboxylic acids |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0097978B1 (en) |
| JP (1) | JPS597130A (en) |
| AU (1) | AU554325B2 (en) |
| CA (1) | CA1226299A (en) |
| DE (1) | DE3361551D1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8204883A (en) * | 1982-12-17 | 1984-07-16 | Shell Int Research | PROCESS FOR THE PREPARATION OF CARBONIC ACID ANHYDRIDES |
| CA1218999A (en) * | 1983-01-25 | 1987-03-10 | Eit Drent | Process for the preparation of carboxylic acids and/or esters |
| CA1226300A (en) * | 1983-03-02 | 1987-09-01 | Eit Drent | Process for the preparation of carboxylic acids |
| CA1231966A (en) * | 1983-12-02 | 1988-01-26 | David J. Schreck | Production of carboxylic acids from alcohols |
| CA1231965A (en) * | 1983-12-02 | 1988-01-26 | David J. Schreck | Synergistic production of carboxylic acids from alcohols |
| CA1231964A (en) * | 1983-12-02 | 1988-01-26 | David J. Schreck | Synergistic production of carboxylic acids from organic formate esters |
| CA1252480A (en) * | 1984-07-20 | 1989-04-11 | Richard W. Wegman | Production of carboxylic acids from organic formate esters using rhodium complex catalysts |
| CA1237728A (en) * | 1984-07-20 | 1988-06-07 | Anthony G. Abatjoglou | Production of carboxylic acids from alcohols using rhodium complex catalysts |
| US5817869A (en) * | 1995-10-03 | 1998-10-06 | Quantum Chemical Corporation | Use of pentavalent Group VA oxides in acetic acid processing |
| US6031129A (en) * | 1995-10-03 | 2000-02-29 | Quantum Chemical Corporation | Use of pentavalent group VA oxides in acetic acid processing |
| GB9802027D0 (en) * | 1998-01-31 | 1998-03-25 | Bp Chem Int Ltd | Chemical process |
| CN1113845C (en) * | 1998-05-27 | 2003-07-09 | 千年石油化工公司 | Use of pentavalent group VA oxides in acetic acid processing |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6906324A (en) * | 1968-04-25 | 1969-10-28 | ||
| SE413891B (en) * | 1973-09-04 | 1980-06-30 | Halcon International Inc | SET TO MAKE AN ANHYDRID OF A MONOCARBONIC ACID. |
| DE2450965C2 (en) * | 1974-10-26 | 1983-06-09 | Hoechst Ag, 6230 Frankfurt | Process for the production of acetic anhydride |
| SE426583B (en) * | 1975-03-10 | 1983-01-31 | Halcon Res & Dev | SET TO MAKE ETHYLIDEN ACETATE |
-
1983
- 1983-05-25 EP EP83200745A patent/EP0097978B1/en not_active Expired
- 1983-05-25 DE DE8383200745T patent/DE3361551D1/en not_active Expired
- 1983-05-27 CA CA000429102A patent/CA1226299A/en not_active Expired
- 1983-06-16 JP JP10683283A patent/JPS597130A/en active Pending
- 1983-06-16 AU AU15848/83A patent/AU554325B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| AU554325B2 (en) | 1986-08-14 |
| JPS597130A (en) | 1984-01-14 |
| AU1584883A (en) | 1983-12-22 |
| DE3361551D1 (en) | 1986-01-30 |
| EP0097978A1 (en) | 1984-01-11 |
| EP0097978B1 (en) | 1985-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1226299A (en) | Process for the co-production of carboxylic acids | |
| JPS5982336A (en) | Carbonylation of olefin unsaturated compound by palladium catalyst | |
| US4306091A (en) | Process for the preparation of acetaldehyde | |
| GB2146637A (en) | Producing carboxylic acids by carbonylation | |
| EP0153834B1 (en) | Carbonylation process improvement | |
| US4205190A (en) | Process for the hydrocarbonylation of methanol to ethanol in the presence of added oxygen-containing organic compounds | |
| JPS5826842A (en) | Carbonate ester manufacture | |
| EP0114703A1 (en) | Process for the preparation of carboxylic acids and/or esters | |
| CA1194033A (en) | Process for the co-production of carboxylic acids and carboxylic acid esters | |
| US4374752A (en) | Catalyst and process for the conversion of methanol to acetaldehyde | |
| GB2059794A (en) | Process for preparing carboxylic acid anhydrides | |
| GB2089804A (en) | Preparation of carboxylic acid anhydrides | |
| US4409404A (en) | Process for producing ethanol using said novel catalyst system | |
| GB2024811A (en) | Manufacturers of vicinal glycol esters from synthesis gas | |
| EP0310168B1 (en) | Process for the preparation of esters of carboxylic acids | |
| EP0037586B1 (en) | Process for the selective hydroformylation of methanol to acetaldehyde | |
| US4563309A (en) | Production of carboxylic anhydrides from methyl carboxlyates using rhodium complex catalysts | |
| GB2128609A (en) | Preparations of carboxylic acids | |
| EP0155122A2 (en) | Production of esters | |
| EP0034374B1 (en) | Selective homologation of acetals or ethers to monohydric or polyhydric alcohols | |
| CA1105060A (en) | Hydrocarbonylation of methanol to ethanol in the presence of added compounds | |
| CA1218998A (en) | Process for the preparation of ethylidene diacetate and/or acetic acid anhydride | |
| CA1228865A (en) | Process for the preparation of carboxylic acids and/or esters | |
| CA1187097A (en) | Process for the co-production of carboxylic acids and carboxylic acid esters | |
| CA1234146A (en) | Preparation of carboxylic acids and esters |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |